An attractive source of renewable green energy, the catalytic interconversion of ammonia (NH3) and nitrogen (N2) represents a critical transformation for sustainable carbon-free fuels. Understanding the structure and reactivity of dinitrogen (N2), diazene (N2H2), and hydrazine (N2H4) intermediates at dinuclear metal sites may provide important mechanistic clues to developing efficient, low barrier N-H and N-N bond forming and cleaving catalytic processes in the interconversion of NH3 and N2. We describe new families of dinuclear b-diketiminato complexes motivated by our lab’s recent success employing b-diketiminato copper catalysts for ammonia oxidation that bimolecularly form N-N bonds via [CuII]-NH2 intermediates. Using linkers that control the relative geometry of two b-diketiminato metal centers [M] in close proximity (2.5 – 3.3 Å), we describe the synthesis and reactivity of new copper(I) complexes and their interaction with N2, N2H2, and N2H4. We also describe exploratory studies that extend these concepts to more reducing metals such as Co, Ni, and Fe to understand the role of the metal’s d-electron count in the structure and reactivity with nitrogenous ligands relevant to the interconversion of NH3 and N2.

Bimetallic complexes in the interconversion of N2 and NH3

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ACS Fall 2022

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